The present invention relates to dyeing compositions comprising a combination of two specific cationic dyes and not containing a self-oxidizing agent, to the use of the compositions as direct dyes in dyeing applications for keratin fibers, and in particular human keratin fibers such as the hair, to direct dyeing processes using the compositions, and to dyeing devices using the compositions.
Two types of dyeing can be distinguished in the hair field.
The first is permanent dyeing or oxidation dyeing, which uses oxidation dyes that develop their dyeing power in the presence of oxidizing agents.
The second is semi-permanent or temporary dyeing, or direct dyeing, which uses dyes capable of giving the hair""s natural color a more or less pronounced color change which may be able to withstand shampooing several times. These dyes are referred to as direct dyes; they can be used with or without an oxidizing agent. In the presence of an oxidizing agent, the dyeing is referred to as lightening; without an oxidizing agent, the dyeing is referred to as conventional direct dyeing rather than lightening dyeing.
The present invention relates to conventional direct dyeing, i.e., dyeing without an oxidizing agent, which is less aggressive towards keratin fibers.
Among the cationic direct dyes available for dyeing keratin fibers, in particular human keratin fibers, the compounds of formulae (I) to (III) defined below are already known. However, these dyes, generally referred to as Arianor dyes, give dyeing results which have properties that are insufficient with regard to the intensity and chromaticity of the shades obtained, the homogeneity of the color distributed along the fiber (the dyeing is then said to be too selective), and the staying power in terms of fastness with respect to the various attacking factors to which the hair may be subjected (e.g., light, bad weather, shampooing).
The inventor has just discovered, entirely surprisingly and unexpectedly, that a combination of at least one cationic dye of formulae (I) to (III) defined below and of at least one cationic dye of formulae (IV) to (VII) defined below is suitable for direct dyeing, and that, in addition, it makes it possible to obtain dye compositions which give relatively unselective and highly chromatic dyeing results that are particularly fast with respect to the various attacking factors to which the hair may be subjected.
This discovery forms the basis of the present invention.
A first subject of the present invention is thus the use, as a direct dye in, or for the manufacture of, direct dyeing compositions for keratin fibers and in particular for human keratin fibers such as the hair, of a combination comprising (i) at least one cationic dye of formulae (I) to (III) defined below, and (ii) at least one cationic dye of formulae (IV) to (VII) defined below, it being understood that the direct dyeing compositions do not contain a self-oxidizing dye:
(i) cationic dye of formulae (I), (II) and (III): 
in which:
R1 represents a hydrogen atom or an amino radical;
R2 represents a hydrogen atom or a nitro group;
R3 represents a hydrogen atom, a nitro group or a C1-C4 alkoxy radical;
R4 represents a C1-C4 alkyl radical;
R5 represents a hydrogen atom or a para-tri(C1-C4)alkylammoniophenyl group;
R6 represents a bromine atom or an NH-para-tri-(C1-C4)alkylammoniophenyl group; and
Xxe2x88x92 represents an anion preferably chosen from chloride, methylsulphate and acetate.
According to the present invention, the compounds corresponding to the mesomeric forms of structures (I) to (III) can also be used.
As examples of compounds of formula (I), mention may be made of the dyes Basic Brown 16, Basic Red 76, Basic Brown 17 and Basic Red 118.
As an example of compounds of formula (II), mention may be made of the dye Basic Yellow 57.
As an example of compounds of formula (III), mention may be made of the dye Basic Blue 99.
These Color Index names cover the following chemical structures (in the form of their chlorides):
8-((4-aminophenyl)azo)-7-hydroxy-2-trimethylammonionaphthalene,
8-((2-methoxyphenyl)azo)-7-hydroxy-2-trimethylammonionaphthalene,
8-((4-amino nitrophenyl)azo)-7-hydroxy-2-trimethylammonionaphthalene,
8-((4-amino-2-nitrophenyl)azo)-7-hydroxy-2-trimethylammonionaphthalene,
3-((3-methyl-5-hydroxy-1-phenyl-1H-pyrazol-4-yl)azo) trimethylammoniobenzene,
3-((4-amino-6-bromo-5,8-dihydro-1-hydroxy-8-imino-5-oxo-2-naphthyl)amino)trimethylammoniobenzene, and
3-((3,7-dibromo-5,8-dihydro-4-hydroxy-5-imino-8-oxo-1-naphthyl)amino)trimethylammoniobenzene.
The compounds of formulae (I) to (III) are found, alone or in combination, in the products corresponding to the trade names, sold by the company Warner Jenkinson: Arianor Mahogany, Arianor Steel Blue, Arianor Madder Red, Arianor Sienna Brown, Arianor Straw Yellow and Arianor Bordeaux.
(ii) cationic dye of formulae (IV), (V), (VI), (VIxe2x80x2) and (VII) below:
a) compounds of formula (IV): 
xe2x80x83in which:
D represents a nitrogen atom or a xe2x80x94CH group,
R7 and R8, which may be identical or different, represent a hydrogen atom; a 4xe2x80x2-aminophenyl radical; or a C1-C4 alkyl radical which can be substituted with a xe2x80x94CN, xe2x80x94OH or xe2x80x94NH2 radical, or which can form, with the nitrogen atom to which it is attached and with a carbon atom of the benzene ring, a heterocycle optionally comprising oxygen or additional nitrogen atoms and which can be substituted with one or more C1-C4 alkyl radicals;
R9 and Rxe2x80x29, which may be identical or different, represent a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, or a cyano, C1-C4 alkyl, C1-C4 alkoxy or acetyloxy radical;
Xxe2x88x92 represents an anion preferably chosen from chloride, methylsulphate and acetate; and
A represents a group chosen from the structures A1 to A19 below: 
xe2x80x83in which:
R10 represents a C1-C4 alkyl radical which can be substituted with a hydroxyl radical; and
R11 represents a C1-C4 alkoxy radical;
with the provisos that:
(i) when D represents xe2x80x94CH, and A represents A4 or A13, and R9 is other than an alkoxy radical, then R7 and R8 do not simultaneously denote a hydrogen atom; and
(ii) when D represents a nitrogen atom, and A represents A6, then R7 and R8 do not simultaneously denote a methyl radical.
b) compounds of formula (V): 
xe2x80x83in which:
R12 represents a hydrogen atom or a C1-C4 alkyl radical;
R13 represents a hydrogen atom, an alkyl radical which can be substituted with a xe2x80x94CN radical or with an amino group, or a 4xe2x80x2-aminophenyl radical; or R13 forms, together with R12 and the nitrogen atom to which they are attached, a heterocycle optionally comprising oxygen and/or nitrogen, and which can be substituted with a C1-C4 alkyl radical;
R14 and R15, which may be identical or different, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine and fluorine, a C1-C4 alkyl or C1-C4 alkoxy radical or a xe2x80x94CN radical;
Xxe2x88x92 represents an anion preferably chosen from chloride, methyl sulphate and acetate; and
B represents a group chosen from the structures B1 to B6 below: 
xe2x80x83in which:
R16 represents a C1-C4 alkyl radical; and
R16 and R17, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical;
(c) compounds of formulae (VI) and (VIxe2x80x2): 
xe2x80x83in which:
R19 represents a hydrogen atom, a C1-C4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine and fluorine or an amino radical;
R20 represents a hydrogen atom or a C1-C4 alkyl radical, or forms, with the nitrogen atom to which it is attached and a carbon atom of the benzene ring, a heterocycle optionally containing oxygen and/or substituted with one or more identical or different C1-C4 alkyl groups;
R21 represents a hydrogen or halogen atom such as bromine, chlorine, iodine or fluorine;
R22 and R23, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical;
D1 and D2, which may be identical or different, represent a nitrogen atom or a xe2x80x94CH group;
m is equal to 0 or 1;
Xxe2x88x92 represents an anion preferably chosen from chloride, methyl sulphate and acetate; and
E represents a group chosen from the structures E1 to E8 below: 
xe2x80x83in which Rxe2x80x2 represents a C1-C4 alkyl radical;
when m is equal to 0 and D1 represents a nitrogen atom, then E can also denote a group of structure E9 below: 
xe2x80x83in which Rxe2x80x2 represents a C1-C4 alkyl radical; it being understood that when R19 represents an unsubstituted amino group, then D1 and D2 simultaneously represent a xe2x80x94CH group and m is equal to 0;
d) compounds of formula (VII):
Gxe2x80x94Nxe2x95x90Nxe2x80x94Jxe2x80x83xe2x80x83(VII)
xe2x80x83in which:
G represents a group chosen from the structures G1 to G3 below: 
xe2x80x83in which:
R24 denotes a C1-C4 alkyl radical, a phenyl radical which can be substituted with a C1-C4 alkyl radical or a halogen atom chosen from chlorine, bromine, iodine and fluorine
R25 denotes a C1-C4 alkyl radical or a phenyl radical;
R26 and R27, which may be identical or different, represent a C1-C4 alkyl radical or a phenyl radical; or R26 and R27 together form, in G1, a benzene ring substituted with one or more identical or different C1-C4 alkyl C1-C4 alkoxy or NO2 radicals; or R26 and R27 together form, in G2, a benzene ring optionally substituted with one or more identical or different C1-C4 alkyl, C1-C4 alkoxy or NO2 radicals;
R26 can also denote a hydrogen atom;
Z denotes an oxygen or sulphur atom or a group xe2x80x94NR25;
M represents a xe2x80x94CH, xe2x80x94CR in which R denotes C1-C4 alkyl, or xe2x80x94NR28(Xxe2x88x92)r group;
K represents a xe2x80x94CH, xe2x80x94CR in which R denotes C1-C4 alkyl, or xe2x80x94NR28(Xxe2x88x92)r group;
P represents a xe2x80x94CH, xe2x80x94CR in which R denotes C1-C4 alkyl, or xe2x80x94NR28(Xxe2x88x92)r group;
r denotes zero or 1;
R28 represents an atom Oxe2x88x92, a C1-C4 alkoxy radical or a C1-C4 alkyl radical;
R29 and R30, which may be identical or different, represent a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl or C1-C4 alkoxy radical or an xe2x80x94NO2 radical;
Xxe2x88x92 represents an anion preferably chosen from chloride, iodide, methyl sulphate, ethyl sulphate, acetate and perchlorate;
with the proviso that:
if R28 denotes Oxe2x88x92, then r denotes zero;
if K or P or M denotes C1-C4 xe2x80x94N-alkyl Xxe2x88x92, then R29 or R30 is other than a hydrogen atom;
if K denotes xe2x80x94NR28(Xxe2x88x92)r, then Mxe2x95x90P and denotes xe2x80x94CH or xe2x80x94CR;
if M denotes xe2x80x94NR28(Xxe2x88x92)r, then Kxe2x95x90P and denotes xe2x80x94CH or xe2x80x94CR;
if P denotes xe2x80x94NR28(Xxe2x88x92)r, then Kxe2x95x90M and denotes xe2x80x94CH or xe2x80x94CR;
if Z denotes a sulphur atom and R27 denotes C1-C4 alkyl, then R26 is other than a hydrogen atom; and
if Z denotes xe2x80x94NR28 and R25 denotes C1-C4 alkyl, then at least one of the radicals R24, R26 or R27 of G2 is other than a C1-C4 alkyl radical;
J represents:
(a) a group of structure J1 below: 
xe2x80x83in which:
R31 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl or C1-C4 alkoxy radical, or an xe2x80x94OH, xe2x80x94NO2, xe2x80x94NHR34, xe2x80x94NR35R36 or C1-C4xe2x80x94NHCO alkyl radical; or R31 forms, together with R32, a 5- or 6-membered ring optionally comprising one or more identical or different hetero atoms chosen from nitrogen, oxygen and sulphur;
R32 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, or a C1-C4 alkyl or C1-C4 alkoxy radical; or R32 forms, with R33 or R34, a 5- or 6-membered ring optionally comprising one or more identical or different hetero atoms chosen from nitrogen, oxygen and sulphur;
R33 represents a hydrogen atom, an xe2x80x94OH radical, an xe2x80x94NHR34 radical or an xe2x80x94NR35R36 radical;
R34 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical or a phenyl radical;
R35 and R36, which may be identical or different, represent a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical or a C2-C4 polyhydroxyalkyl radical;
xe2x80x83or
(b) a 5- or 6-membered nitrogenous heterocyclic group which can contain other hetero atoms and/or carbonyl groups and which can be substituted with one or more identical or different C1-C4 alkyl, amino or phenyl radicals, and in particular a group of structure J2 below: 
xe2x80x83in which:
R37 and R38, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a phenyl radical; 
Y denotes a xe2x80x94CO-radical or a radical
n is equal to 0 or 1; and
U denotes a xe2x80x94COxe2x80x94 radical when n is equal to 1.
Compounds corresponding to the mesomeric forms of the structures (IV) to (VII) can also be used.
In the structures (IV) to (VII), as in the structures (I) to (III) defined above, the C1-C4 alkyl or alkoxy group preferably denotes methyl, ethyl, butyl, methoxy or ethoxy.
The cationic direct dyes of formulae (IV), (V), (VI) and (VIxe2x80x2) which can be used in the dye compositions in accordance with the invention are known compounds and are described, for example, in patent applications WO 95/01772, WO 95/15144 and EP-A-0 714 954, the disclosures of which are incorporated by reference herein. The cationic direct dyes of formula (VII) which can be used in the dye compositions according to the invention are known compounds and are described, for example, in patent applications FR-2 189 006, FR-2 285 851 and FR-2 140 205 and the certificates of addition thereof, the disclosures of which are incorporated by reference herein.
Among the cationic direct dyes of formula (IV) which can be used in the dye compositions according to the invention, mention may be made more particularly of the compounds corresponding to the structures (IV1) to (IV54) below: 
Among the compounds of the structures (IV1) to (IV54) described above, those most particularly preferred are the compounds corresponding to the structures (IV1), (IV2), (IV14) and (IV31).
Among the cationic direct dyes of formula (V) which can be used in the dye compositions according to the invention, mention may be made more particularly of the compounds corresponding to the structures (V1) to (V9) below: 
Among the cationic direct dyes of formula (VI) which can be used in the dye compositions according to the invention, mention may be made more particularly of the compounds corresponding to the structures (VI1) to (VI18) below: 
Among the specific compounds of the structures (VI1) to (VI18) described above, those most particularly preferred are the compounds corresponding to the structures (VI4), (VI5) and (VI13).
Among the cationic direct dyes of formula (VIxe2x80x2) which can be used in the dye compositions according to the invention, mention may be made more particularly of the compounds corresponding to the structures (VIxe2x80x21) to (VIxe2x80x23) below: 
Among the cationic direct dyes of formula (VII) which can be used in the dye compositions according to the invention, mention may be made more particularly of the compounds of the structures (VII1) to (VII77) below: 
Another subject of the invention is a composition for the direct dyeing of keratin fibers, in particular human keratin fibers such as the hair, comprising, in a medium suitable for dyeing, a combination of cationic dyes of formulae (I) to (VII) as defined above, it being understand that the composition does not contain a self-oxidizing dye.
The cationic dye(s) of formulae (I) to (III) used according to the invention preferably represent from 0.001 to 10% by weight approximately relative to the total weight of the direct dye composition, and even more preferably from 0.005 to 5% by weight approximately relative to this weight.
The cationic dye(s) of formula (IV) to (VII) used according to the invention preferably represent from 0.001 to 10% by weight approximately relative to the total weight of the direct dye composition, and even more preferably from 0.005 to 5% by weight approximately relative to this weight.
The combination of cationic dyes of formulae (I) to (VII) according to the invention can also be used, as direct dyes, in well-known oxidation dyeing processes using oxidation dyes (oxidation dye precursors and optionally couplers), to vary the shades of the dyeing results obtained with the oxidation dyes or to enrich the dyeing results with glints.
In addition to the combination of cationic dyes of formulae (I) to (VII) according to the invention, the dye composition according to the invention can also contain, to broaden the range of shades and to obtain varied tints, other direct dyes conventionally used, in particular nitrobenzene dyes, anthraquinone dyes, naphthoquinone dyes, triarylmethane dyes, xanthine dyes and azo dyes that are non-cationic.
The medium suitable for dyeing (or support) generally comprises water or a I mixture of water and at least one organic solvent to dissolve the compounds which would not be sufficiently water-soluble. Organic solvents which may be mentioned, for example, are C1-C4 lower alkanols, such as ethanol and isopropanol, and aromatic alcohols such as benzyl alcohol, as well as similar products and mixtures thereof.
The solvents can be present in proportions preferably ranging from 1 to 40% by weight approximately relative to the total weight of the dye composition, and even more preferably from 5 to 30% by weight approximately.
The pH of the dye composition according to the invention ranges generally from 2 to 11 approximately, and preferably from 5 to 10 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibers.
Among the acidifying agents which may be mentioned, by way of example, are inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid and sulphonic acids.
Among the basifying agents which may be mentioned, for example, are aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine as well as derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (VIII) below: 
in which W is a propylene residue optionally substituted with a hydroxyl group or a C1-C6 alkyl radical; and R39, R40, R41 and R42, which may be identical or different, represent a hydrogen atom or a C1-C6 alkyl or C1-C6 hydroxyalkyl radical.
The direct dye composition according to the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair, such as antioxidants, penetrating agents, sequestering agents, thickeners, fragrances, buffers, dispersants, anionic, nonionic, cationic or amphoteric surfactants, cationic, anionic, nonionic or amphoteric polymers, film-forming agents, ceramides, preserving agents, screening agents and opacifiers.
Needless to say, the person skilled in the art will select the optional additional compound(s) such that the advantageous properties associated with the dye composition according to the invention are not, or are not substantially, adversely affected by the addition(s).
The direct dye composition according to the invention can be in various forms, such as liquids, shampoos, creams or gels or in any other form which is suitable for dyeing keratin fibers, and in particular human hair. It can be obtained by mixing together, at the time of use, a composition, which may be pulverulent, containing a combination of cationic dyes of formulae (I) to (VII) defined above with an aqueous composition.
Another subject of the invention is a process for the direct dyeing of keratin fibers, and in particular of human keratin fibers such as the hair, using the dye composition as defined above.
According to a first variant of this direct dyeing process according to the invention, at least one dye composition as defined above is applied to the fibers, for a period which is sufficient to develop the desired dyeing results, after which the fibers are rinsed, optionally washed with shampoo and rinsed again, and dried.
The time required to develop the dyeing result on the keratin fibers ranges generally from 3 to 60 minutes and even more specifically from 5 to 40 minutes.
According to a second variant of this direct dyeing process according to the invention, at least one dye composition as defined above is applied to the fibers, for a period which is sufficient to develop the desired dyeing results, and dried without final rinsing.
Another subject of the invention is a multi-compartment dyeing device or xe2x80x9ckitxe2x80x9d or any other multi-compartment packaging system, a first compartment of which contains a composition containing the cationic dye of formulae (I) to (III) defined above, and a second compartment of which contains a composition containing the cationic dye of formulae (IV) to (VII) defined above. In one variant of the invention, the first compartment contains a pulverulent composition containing a combination of at least one cationic dye of formulae (I) to (III) and at least one cationic dye of formulae (IV) to (VII), and the second compartment contains an aqueous composition used as a vehicle for the dyeing operation. These devices can be equipped with a means for applying the desired mixture to the hair, such as the devices described in patent FR-2 586 913, the disclosure of which is incorporated by reference herein.